Composition and method for stimulating seed germination and plant growths



United States Patent 3,331,678 COMPOSITION AND BETHOD FOR STIIVIULATING SEED GERIVIINATION AND PLANT GROWTHS Cecil C. Chappelow, Jr., 7111 Summit, Kansas City, Mo. 64114, and Thomas J. Byerley, 5100 Maple, Shawnee Mission, Kans. 66202 No Drawing. Filed May 9, 1966, Ser. No. 548,379 20 Claims. (CI. 71-77) This application is a continuation-in-part of our copending application, Ser. No. 284,841, filed June 3, 1963, and now abandoned.

This invention relates to new organic triaryl dideoXy hexitols and to compositions for and methods of stimulating seed germination, root and plant growth.

It has heretofore been proposed to treat seeds with hormones to increase the percentage of germination and to have a systemic effect on the new plant; that is, to influence growth and yield of the plant. While there have been isolated instances of the efiicacy of hormones for this purpose, hormones have been found to be much more effective in the destruction of seeds, particularly for the destruction of weed seeds and weeds, than for stimulating the germination of the seeds or the growth of the plants. Certain chemical compounds (other than hormones) are, however, alleged to have plant growth promoting properties. Patent No. 2,842,051, dated July 8, 1959, for instance, discloses mixtures having plant growth promoting properties that include gibberellic acid, or an active derivative thereof, and a diluent. The diluent, so that patent states, may be liquid or solid or may consist of or contain plant nutrients, particularly sources of nitrogen.

We have now discovered that triaryl dideoxy hexitols have a stimulating effect upon the germination of seeds and upon the growth of roots and plants. Some of these compounds can be made in accordance with methods disclosed in the Linn Patent No. 2,798,100, dated July 2, 1957, for the making of compounds that are therein termed diaryldesoxy ketitols and are herein more accurately termed triaryl dideoxy ketitols. This class of compounds can be produced by reacting a ketose sugar with an aromatic compound, using hydrogen fluoride as a catalyst.

We have further discovered that mixed triaryl dideoxy ketitols wherein at least one aryl differs from the other aryl radicals and mixed cycloalkyl aryl dideoxy ketitols wherein one or two of the aryls have been selectively hydrogenated also have a seed stimulating and plant growth stimulating activity.

Examples of ketose sugares useful herein are the monosaccharides containing a ketone group such as fructose, sorbose and various isomeric forms thereof. Among the simpler aromatic hydrocarbons are benzene, toluene, o- Xylene, m-xylene, p-xylene, ethyl benzene and 1,2,3-trimethyl benzene. The condensation products are generically referred to as triaryl dideoxy ketitols of which 1,1,2-tris (4-methylphenyl)-l,2-dideoxy heXitol is a species. While some of the compounds prepared by the Linn method are old, a more accurate structure only being restated, others as further described and claimed below, are new.

We have also found quite unexpectedly that the triaryl dideoxy compounds have unusual utility for stimulating plant seed germination and plant growth. We have further found that these compounds may be employed both in discrete particle form as dusts, and also in aqueous-type dispersions, or in the form of'wettable powders containing a dispersant for dispersing the relatively water-insoluble active compound into colloidal solution or suspension. Preparations containing the active compound can be used both in the water culture of plants, referred to as hydroponics, and in the surface soil culture of plants. A large number of different types of plants have been found to be benefited by the application of the active compounds to the seeds, roots, or plants themselves.

It is therefore an important object of this invention to provide a novel method of stimulating the germination of plant seeds and the growth of roots and plants, and to provide new compounds and new compositions suitable for application to the seeds, roots or plants, in order to realize the stimulating growth properties of the active compound.

Other and further important objects of this invention will become apparent from the following description and appended claims.

The various active compounds to which this invention is directed may be generically termed the condensation products of monosaccharides having a ketone group and benzene hydrocarbons, including the alkyl-, hydroxyand alkylhydroxy benzenes, mixed alkyl hydrocarbons of benzene and cyclo-alkyl benzene hydrocarbons.

The following generic formula defines compounds having useful stimulating effects upon seed germination and upon the growth of roots and plants:

1 Ar-CH-Ar Hz-X wherein Ar is a phenyl, alkylphenyl, hydroxy phenyl or alkyl hydroxy phenyl radical; Ar' and Ar" are phenyl, alkylphenyl, hydroxy phenyl, alkyl hydroxy phenyl, cyclohexyl, alkyl cyclohexyl, hydroxy cyclohexyl or alkyl hydroxy cyclohexyl radicals; X is OR, -OOCR, OCOOR, OCONR and two X radicals may form a cyclic dioXy alkylidene ether of the formula R is H, and alkyl or aryl radical having 1 to 10 carbon atoms; R is an alkyl or aryl radical having 1 to 10 carbon atoms; and R" is an alkylidene or an alkylidene aryl radical having 1 to 10 carbon atoms.

In the above formula where Ar, Ar and Ar are different radicals or when X is carbonyl (OCOOR), carbamoyl (OCONR or alkylidene or alkylidene aryl novel compounds are defined which may be given bv the following subgeneric formula:

I ArCHAr' HAr CHX n-X wherein Ar, Ar and Ar" are the same as given above, at least one radical differing from another; one or more X radicals are --OCOOR, OCONR 3 Where Ar, Ar'-and Ar" are the same and X is as defined in Formula I but not in Formula II above, the com- (2) The acetylated condensation product of D-fructose and toluene, M.P. 157.5-l58.5 C., [a] 1.3 (c. 2, acetone); in which Ar is p-CH C H and Xjs OOCR, and R is CH viZ, a 1,l,2-tris(4-methylphenyl)-1,2- dideoxy-3,4,5,6 tetra-O-acetyl hexitol.

(3) The condensation product of D-fructose and o- Xylene, M.P. 205-207" C., [a] |40.5 (c. 2, acetone); in which Ar is m-, p (CH C H and X is OH; viz, a l, l ,Z-tris 3 ,4-dimethylphenyl -l,2-dideoxy hexitol. (4) The condensation product of L-sorbose and toluene, M.P. 215.52l7 C., in which Ar is p-CH C H and X is OH; viz, a l,1,2-tris(4-methylphenyl)-l,2-dideoxy hexi-tol. a

(5) The condensation product of L-sorbose and o- Xylene, M.P. 2l2-2l4 C., [a] +l5.9 (c. 2, dimethylformamidc); in which AI is m-, p-(CH C H and X is OH; viz, a 1,1,2-tris(3,4-diethylphenyl)-1,2-dideoxy hexitol;

(6) The acetylated condsation product of D-fructose and o-xylene, M.P. 184185.5 C., [a] -[10.2 (c. 2, acetone); in which Ar is m-, p-(CH C H and X is OOCH and R is CH viz, a 1,1,2 tris(3,4-dimethylphenyl)-1,2-dideoxy-3,4,5,6-tetraO-acetyl hexitol.

(7) The methylated condensation product of D-fructose and toluene, B.P. 220-224 C./ 0.1 mm. Hg,

64.9 (c. 2, acetone); in which AI is p-CH C H and X is OR and R is CH viz, a 1,l,2-tris(4-methylphenyl) -1,2-dideoXy-3,4,5,6-tetra-O-metlhyl hexitoh Preparation of mixed triaryl dideoxy ketitols (A) The mixed aryl ketitol is prepared by first forming a 2-monoaryl Z-deoxy pyr-anose, known compounds, where the 2-mono-aryl group is Ar" as defined above, which in about molar quantity is reacted with about 2 mols of a difierent aryl group Ar as defined above in the presence of a large excess of anhydrous hydrogen fluoride at low temperatures of about -'50 to C.

Preparation of a carbamate derivative (B) Where X is a carbamoyl radical the triaryl dideoxy ketitol, X=OH, is reacted with an aryl isocyanate using pyridine as catalyst according to the following:

Preparation of a carbonate derivative (C) Where X is a carbonate radical, the triaryl dideoxy ketitol condensate (III) is converted to the tris lithium alcoholate (V) form; then converted to tris alkoxy carbonyl (VI) with alkyl chloroiorrnate which undergoes intrornolecular cyclization (VII) or (VIII) as follows:

and Ar, Ar, Ar" and R are defined in the generic Formula 1 above.

Preparation of dioxy cyclic ether alkylidene or alkyliaene phenyl '(D) The two X groups combine to form a dioxy alkyl-- where R", Ar, Ar and Ar" are as definedin I above.

Preparation of a, partial alkoxylated derivative (E) Where partial alkoxylation is desired, the tri-aryl dideoxy ketitol condensate (III) is treated with the desired dihydrocarbon sulfate ester according to the following reaction:

Preparation of cycloallcyl aryl mixed compound (F) Where one or two ofthe a-ryls are desirably converted to cycle alkyl, the triaryl dideoxy ketitol condemsate or its selected X derivative is selectively hydrogenated EXAMPLE 1 Preparation of a homo tri aryl dideoxy hexitol A charge of 75 grams (0.42 mole) of L-sorbose and 250 milliliters (220 grams, 2.08 moles) of o-xylene was sealed in a one liter stainless steel Magne Dash autoclave. The autoclave was cooled to below zero, evacuated, and 373 grams of anhydrous hydrogen fluoride added. The mixture was allowed to react at C. for 16 hours, after which time the excess I-H" was removed with a water aspirator for two hours. The autoclave was then opened and the contents diluted with anhydrous ether. The ethereal solution was washed with water until neutral, and dried over anhydrous Na SO Addition of n-pentane to the ether solution caused the precipitation of 56 grams of crude product. After washing with n-pentane and cold 'benzene, the partially purified product was recrystallized once from methyl alcohol. One subsequent recrystallization from toluene yielded 30 grams of the final product, 1,1,2-tris(3,4-dimethylphenyl)-1,2-dideoxy hexitol, as a white crystalline powder, M.P. 213-214 C., [0c] +13.6

(c. 2, DMF).

Analysis.-Calcd. for G l-1 0 C, 77.89; H, 8.28. Found: C, 77.96; H, 8.04.

Following the procedure of Example 1, the condensa tion product of D-fructose and benzene is obtained With an M.P. of 205208 C., [a] +54.36 (c. 2, DMF); in which Ar is C H and X is OH; viz, 1,1,2-tri-phenyl-L2- dideoxy hexitol.

Following the procedure of Example 1, the condensation product of D-fructose and ethylbenzene is obtained with an M.P. of 155l58 C.; in which Ar is p-C H C H and X is OH; viz, 1,1,2-tris(4-ethylphenyl)-1,2-dideoxy hexitol.

EXAMPLE 2 Mixed tri aryl dideoxy hexitol A charge of 48 grams (0.18 mole) of a 2-(3,4-dimethyl)-2-deoxy-D-fructopyranose, M.P. 136-138 C., and 350 grams of toluene were placed in a one liter round-bottom flask, equipped with a stirrer, thermometer, Dean Stark trap and condenser. The mixture was heated to reflux and a small trace of moisture removed. The toluene slurry was transferred to a one liter stainless steel Magne Dash autoclave, sealed, cooled to 30 C., evacuated and 350 grams (17.9 moles) of anhydrous hydrogen fluoride added. The mixture was then reacted at 1 C. for three hours. The excess hydrogen fluoride was removed with a water pump for two hours, after which the autoclave was opened, diluted with ether and transferred to a separatory funnel. The ethereal solution was washed with water until neutral and evaporated to dryness in a hood draft. The residue was washed several times with ether and filtered to yield 18.8 grams of crude product. This was recrystallized four times from boiling benzene to yield 9.0 grams of the final product, a 1,l-bis(4-methylphenyl)-2-(3,4-dimethylphenyl)-l,2-dideoxy hexitol, as a white crystalline solid, M.-P. 186-188 C.

Analysis.Calcd. for C I-1 0 C, 77.39; H, 7.89. Found: C, 77.33; H, 8.21.

EXAMPLE 3 Cyclo alkyl diazyl dideoxy hexilo'l Twenty grams (0.048 mole) of the D-fructose-derived 1,1,2-tris(4-methylphenyl)-l,2-dideoxy hexitol, 100 milliliters of cyclohexane and 10 grams of an activated nickel hydrogenation catalyst were placed in a one liter steel autoclave and pressurized to 835 p.s.i.g. with hydrogen. The contents of the autoclave were stirred at C. for three hours and then the temperature was increased to 125 C. and stirring continued for seventeen hours. The

autoclave was depressurized, opened and the product dissolved in benzene. After filtration to remove the catalyst, the filtrate was evaporated to dryness yielding 15.5 grams of crude product. After a series of successive recrystallizations from acetone-water, isopropyl alcohol, cyclohexane and finally toluene, 2.0 grams of the final product, a 1,2- bis(4 methylphenyl) l (4 methylcyclohexyl) 1,2- dideoxy hexitol, was obtained as a white crystalline powder, M.P. 230233 C. 1

Analysis.-Calcd. for C H O C, 76.02; H, 8.98. Found: C, 75.91; H, 9.16.

EXAMPLE 4 T ri myl dideoxy hexitol acetate To 10 grams of the l,l,-bis(4-ethylphenyl)-2-(3,4-dimethylphenyl)-1,2-dideoxy hexitol which was obtained by the hydrogen fluoride-catalyzed condensation of a 2-(3,4- dirnethylpheuyl)-D-fructopyranose and ethylbenzene, was added 100 grams of acetic anhydride and several drops of concentrated H 30 The mixture was heated on a steam bath for two hours, cooled to room temperature and poured over ice. The water was extracted with ether and the ethereal solution Washed with aqueous K CO solution until neutral. The ethereal solution was then dried over anhydrous Na SO filtered and decolorized with charcoal. The ether was removed on a flash evaporator to yield a viscous dark oil, which solidified on cooling to a crystalline solid. Two recrystallizations from cyclohexane yielded 5 grams of the final product, a l,1-bis(4-ethyl phenyl) 2 (3,4 dimethylphenyl)- 1,2 dideoxy-3,4,5,6- tetra-O-acetyl hexitol, as a white crystalline powder, M.P. 161-164" C.

Analysis.Calcd. for C H O C, 72.36; H, 7.35. Found: C, 72.09; H, 7.11.

EXAMPLE 5 Tri aryl dideoxy hexitol cyclic alkylidene diether Twenty grams (0.058 mole) of the l,l,2-tris(3,4-dimethylphenyl)-1,2-dideoxy hexitol which was obtained by the hydrogen fluoride-catalyzed condensation of D-fructose and o-xylene was dissolved in 200 ml. of dry reagentgrade acetone and placed in a 500 mililitcr three-necked flask. Eight milliliters of concentrated H SO was added, the flask being agitated gently to effect complete solution. The mixture was then stirred vigorously for five hours at room temperature. The reaction mixture was neutralized with aqueous potassium carbonate and concentrated to a heavy syrup on a rotary film evaporator. The syrupy residue was diluted with water and the aqueous solution extracted with benzene. The benzene extracts were dried with anhydrous Na SO decolorized by treatment with charcoal and evaporated to dryness. Three recrystallizations from absolute ethanol yielded 10 grams of the final product, 1,1,2-tris(3,4-dimethylphenyl)-1,2-dideoxy- 3,4:5,6-di-O-isopropylidene hexitol, as White crystals, M.P. 136.0-l37.5 C. a

Analysis.-Calcd. for C H O C, 79.67; H, 8.54. Found: C, 79.75; H, 8.48.

EXAMPLE 6 T ri aryl dideoxy dibenzylz'dine hexitol The reactants consisted of 25 grams (0.08 mole) of the D fructose derived 1,1,2 tris(4 methylphenyl) 1,2- dideoxy hexitol, 13.6 grams (0.10 mole) of zinc chloride and 105 grams (0.9 mole) of benzaldehyde. These starting materials were shaken on a Burrell shaker at 25 C. for twenty four hours in a one liter filter flask. The reaction mixture was worked up by pouring the slurry into 350 milliliters of cold water, and extracting the Water phase several times with Skellysolve F. The extracts were evaporated to dryness and some of the excess benzaldehyde was removed under vacuum at C. The residue was taken up in percent ethanol and decolorized with Norit A. The alcohol filtrate gave 7.2 grams of white crystals,

EXAMPLE 7 V T ri aryl dideoxy hexitol tetra methyl ether The D-fructose-derived 1,1,2-tris(3,4-dimethylphenyl)- 1,2-dideoxy hexitol, 17 grams (0.05 mole) was dissolved in 500 milliliters of hot toluene and 11.5 grams (0.18 mole) of n-butyl-lithium in 115 milliliters of hexane was added. After a slight exothermic reaction during addition,

the mixture was cooled to room temperature and 25.2

grams (0.2 mole) of dimethyl sulfate was added. After the addition, which caused a slight exothermic reaction, the mixture was heated .to reflux and then held at'90 C. over night. The volume of the reaction mixture was then reduced and sufficient base added to destroy the excess dimethyl sulfate. The mixture was heated to 60 C. for one hour, cooled, diluted with water and extracted with ether. The ethereal solution was washed with water until neutral, dried over anhydrous sodium sulfate, decolorized withNorit A and the ether removed on a flash evaporator. Infrared spectrum of the crude compound, a syrup,

contained no hydroxyl bands. This crude product was dissolved in hot absolute methanol, cooled and 6 grams of crystalline precipitate filtered off. The final product, 1,1,2-

'tris(3,4 dimethylphenyl) 1,2 dideoxy 3,4,5,6 tetra- O-methyl hexitol, was a white crystalline solid, M.P. 93.5-95.5 C., [a] ='53.1 (c. 2, acetone).

Analysis-Calcdfor C H O C, 78.72; H, 8.94;

OCH 23.93. Found: C, 78.52; H, 8.88; OCH 23.60.

EXAMPLE 8 Tri aryl dideoxy hexitol carbamaze Ten grams (0.03 mole) of the D-fructose-derived 1,1,2- tris 3,4-dimethylphenyl) -l,2-dideoxy hexitol (M.P. 206.5- 208.5 C.), milliliters (22 grams, 0.185 mole) of phenyl isocyanate, and approximately 3 milliliters of pyridine were placed in a 200 milliliter flask and heated on' the steam bath for forty five minutes. The viscous, oily reaction mixture'was then diluted with 250 milliliters of benzene and washed with cold water. The benzene layer was separated and dried over anhydrous Na SO over- 7 night. The benzene solution Wasevaporated to dryness, and

the residue was taken up in hot cyclohexane. All of the material did not dissolve and the cyclohexane extract was filtered hot. Two and two-tenths grams (M.P. 239-252 C.) removed on the filter while 13.8 grams (M.P. 144- a 160 C.) came out on the cyclohexane filtrate. The latter fraction wasagain heated and stirred with about 700 milliliters of boiling cyclohexane and filtered hot. The filtrate consisted of 8.9 grams (M.P. 167-170 C.). Repeated extractions with cyclohexane yielded 5.0 grams of the final product, 1,1,2tris(3,4-dimethylphenyl)-1,2-dideoxy-3,4,5,6-tetra-O-(phenylcarbamoyl) hexitol, as a white amorphous powder, M.P. 1695-1715 C., [a] +l22.4 (c. 2, acetone).

Analysis.Calcd. for C H N O C, 74.17; H, 6.23; N, 5.97. Found: C, 74.12; H, 6.18; N, 6.29.

EXAMPLE 9 Tri aryl dideoxy hexitol partial ether Fourty-four grams (0.1 mole) of the D-fructose-derived 1,1,2 tris(4-methylphenyl) 1,2-dideoxy 3,45,6- tetra-O-acetyl hexitol was dissolved in 600 milliliters of acetone in a two-liter, three-necked flasleThe stirred solution was heated to 55 C. and a total of 84 milliliters, 0.9

mole)'of dimethylsulfate and 225 milliliters of 30 percent NaOH was added in 10 equal increments at 10 minute intervals. After the 1 0th increment had been added, milliliters ofwater was added, the temperature was'raised to 60 C., and 775 milliliters of solvent were removed. The reaction mixture was poured into a large volume of water and again filtered, Washed with hot water, and taken up in 500 milliliters of diethyl ether. The ether solution was washed several times with water to remove the residual base, decolorized with Norit A, filtered and evaporated to dryness. The crude product amounted to 33 grams of material (M.P. 119-124" C.). Repeated recrystallizations from cyclohexane yielded 15 grams of the final product, 1,l,2-tris('4-methylphenyl)-1,2-dideoxy-5,6- di-O-methyl hexitol, as a white granular solid, M.P. 136.5- 137.5 C., [oc] +25.07 (c. 2, acetone).

Analysis.Calcd. for C H O C, 77.65; H, 8.09; OCH 13.84. Found: C, 77.52; H, 8.06; 0CH 14.24.

EXAMPLE 10 Tri aryl dideoxy hexitol carbonate To 40 grams (0.128 mole) of the D-fructose-derived 1,l,2-tris(4-methylphenyl)-1,2-dideoxy hexitol in 500 milliliters of hot toluene was added 134 milliliters of a 20- percent heptane solution of n-butyllithium (26.8 grams,-

sodium bicarbonate solution and then with water until' it was neutral. After removal of the entrained Water by azeotropic distillation, the resultant clear toluene solu tion was cooled overnight. The white solid which formed was filtered OE and discarded. The filtrate was evaporated to dryness yielding 59 grams of crude product which was recrystallized from absolute ethanol. The white solidthat crystallized out was filtered and dried in a vacuum oven,

to yield 35.5 grams of the final product, 1,1,2-tris(4-methylphenyl) 1,2-dideoxy-3,4-bis-O-(ethoxycarbonyl) 5,6-

cyclo-O-(carbonyl) hexitol, as a white crystalline powder,

M'.P l'66.5l68.0 C.

Analysis.-Ca1cd. for C H O C, 69.14; H, 6.48;

saponification value, 570. Found: C, 69.0; H, 6.4; saponification value, 540. v

In general, the various active compounds encompassed by the generic structural formula herein given are solids that are very sparingly soluble in water. Typically, the water solubilities of the active compounds are in the range of 0.5 to 15 milligrams per 100 grams of cold water, or from 5 to ppm. and of 1.5 to 50 milligrams per 100 grams of boiling water, or from 15 to:

500 p.p.m. Consequently, in order to bring the active compound if used in a dry stateinto effective contact or association with the seed, root or plant to be treated, the active compound should be of a particle size between 100 and 400 mesh, or even finer, and preferably admixed with a solid wettable-type carrier, also in finely divided discrete form, that has the property of causing the resultingdry admixture to adhereto the seed coat. Where the active compound is to be sold and/or used in a water-' dispersed form, a dispersant is admixed with the active compound, or both a dispersant and a carrier, either water-soluble or water-insoluble, are used to effect best results.

The term dispersant as herein used means a substance which promotes the formation of a colloidal solution or suspension of the active compound in a liquid medium, particularly Water. In this broad sense the term is generic to wetting and emulsifying agents that assist in the formation of a colloidal solution or suspension of the active compound used in the treatment of seeds in accordance with the invention.

The term carrier means any normally solid substance, preferably a very finely powdered natural or synthetic siliceous or argillaceous substance, of a hydrated structure and easily wettable. Various tales and clays come under this category, but those that have the specific property of causing the active chemical to adhere to the seed coat should be selected for the purpose.

Examples of suitable dispersants are the following:

Alkali metal (principally sodium) lignosulfates, such as those available under the proprietary names:

Marasperse N and Lignosol XD;

alkali metal (principally sodium) sulfonates of aryl and alkaryl compounds, such as sodium alkylnaphthalene sulfonates available under the proprietary name Nekal BX-78; and

sodium sulfonaphthaleue-urea condensates, such as those available under the proprietary name of Blancol.

Examples of dispersants that have pronounced wetting and emulsifying properties and therefore may be considered primarily as wetting agents or emulsifying agents, or both, are the following:

polyalkoxy or mixed alkoxy (C and C alkoxy radicals) condensates, such as the liquid condensates of which Pluronic L-61 is typical; and the solid condensates of which Pluronic F-68 is typical;

polyethylene glycol fatty esters, such as Alrodyne 304 and Atlox; and

alkaryl sulfonates, such as the sodium alkylbenzene sulfonates, of which Daxad No. 27 is an example;

fatty alcohol polyglycol others, such as Emulgin 05 or 010; and

alkylphenoxy poly (ethyleneoxy) ethanols, such as Igepal DJ-970 and Triton X-l00.

Examples of suitable carriers are the following:

The following are examples of various types of formulations of the active compounds for the purposes indicated, percentages being by weight:

(1) Emulsion concentrates for shipment and subsequent dilution for use in the treatment of seeds, roots and plants Percent Active compound 1-50 Dispersant, such as Triton X-l or Emulgin Aqueous type solvent -50 The aqueous type solvent is suitably a water solution of a low molecular weight (i.e., C -C ketone, alcohol or glycol or mixtures thereof. Such a concentrate is diluted with water to form a suspension, or colloidal dispersion, of the active compound, containing from 1,000 to 10,000 ppm, typically 2,000 ppm. of the active compound, for ultimate use in the treatment of seeds, roots or plants.

(2) Soluble wettable powders for application as such, or for use upon further dilution Percent Active compound 1-75 Carrier, viz, Hi-Sil 232 or Zeolex-7-A 15 Dispersant, such as l-5% Pluronic and 1-5% Lignosol XD, Blancol or Nekal Bx-78 2-10 Soluble diluent such as a powdered sugar or soluble starch 20-95 (3) Insoluble wettable powders for use as such, or for use upon further dilution Percent Active compound l- Carrier, as in 2 above l-5 Dispersant, as in 2 above 2-10 Insoluble carrier, such as a pyrophyllite, talc or clay 20-95 (4) Dusts for application as such to seeds, roots or plants to adhere thereto as dry but wettable dusts Percent Active compound 1-75 Insoluble carrier as in 3 above 25-99 Seed treatment using a wettable powder as dust The active chemical was first incorporated into a wettable powder concentrate containing 50% by weight of the active chemical, and having typically the following formula by weight:

The 50% concentrate was then diluted with a suitable clay, such as Continental Clay, a product of the R. T. Vanderbilt Company, having excellent adherence properties toward seeds, to the following dosage levels: 4%, 2%, 1% and /z% of the active chemical by weight of the admixture.

Seed treatment consisted in admixing with the desired seed a slight excess of the composition at each of the various dosage levels. Prior to planting, the treated seeds were lightly sifted to remove any excess of the treating composition not taken up by the seed coat. This means that while the dosage levels were held constant at the respective percentage levels in the mixing of the treating composition and the seeds, the actual amount of the composition remaining adhered to the seeds after the light sifting operation would vary with the particular seed, due to the size of seed (surface area in proportion to mass), nature of the seed coat and its ability to retain dusts or powders.

The treated seeds were then planted in a soil of a regular potting type. In the preliminary tests, four replicates were always used for each dosage of a particular compound and the observed data were averaged and compared with a planting of the same but untreated seeds, as checks.

Seed treatment using an aqueous type dispersion In this procedure, the active chemical is dispersed in an aqueous type medium as a collodial solution or suspension. This was done by dispersing the just-described wettable powder in Water, or by diluting an emulsion concentrate, such as that described above, to dosage levels of 4,000, 2,000 and 1,000 ppm. of the active compound. These respective solutions or suspensions were then distributed in 5 cc. quantities onto discs of filter paper, con- In the case of sweet corn, all

1 1 tained within plastic petri dishes. Twenty five seeds of the respective selected crops were then placed on each of the treated filter discs; the dishes covered; held at 75 F. for the duration of test and observed for germination on theSth, 7th and 12th day after planting.

As a 'reslult of these two types of test procedures, the active compounds herein specified were found to stimulate seed germination and/ or root and/ or plant growth in the case of the following agricultural crop seeds:

cucumber wheat barley beets (table) buckwheat hybrid grain sorghum flax cotton sweet corn soy beans hybrid corn blue grass rye grass peppers timothy grass sugar beets tomato alfalfa In most cases,'the treatment with an active compound Particular'active compounds have greater effectiveness for one crop seed than another. In the case of corn, for instance, the increase in acceleration of emergence was most pronounced when a /z% dust dosage containing the 1,1,2 tris(4 methylphenyl) 1,2, dideoxy hexitol prepared from D-fructose was applied.

The 1,1,2 tris(4 methylphenyl) 1,2 dieoxy- 3,4,5,6-tetra-O-acetyl hexitol derived from the fructosetoluene condensate showed marked efiect in stimulating the growth of roots and cotyledons.

At the 4,000 p.p.m. dosage level, the D-fructose derived 1,1,2 tris (4 rnethylphenyl) 1,2 dideoxy hexitol exhibited a very pronounced stimulation of the root growth of cucumbers on the 5th and 7th day in that the roots were not only two to three times as long as the check seedlings; but also the root system seemed to be more vigorous and the roots wereidefinitely thicker than the untreated seedlings.

of the specific, active compounds, when applied as dust at a /2% dosage level, showed marked increase in acceleration of emergence. This is highly significant, since corn is such a widely grown crop.

The tetramethoxy derivative of the fructose-toluene condensate, such as the 1,1,2 tris(4-methylphenyl)-l,2 dideoxy 3,4,5,6 tetra-O-methyl hexitol, (Species No. 7 above), exhibits a high degree of stimulatory activity on sugar beets and soy beans, while the fructose-toluene condenate, (Species No. 1 above), and the fructose-O- xylene condensate, (Species No. 3 above), exhibit pronounced regulatory activity on hybrid corn and sorghum.

Maximum germination response of certain types of hybrid seed corn is obtained when a fungicide is used in conjunction with the active stimulator compounds. Any of the conventional fungicides, plant hormones, elemental nutrients and seed disinfectants can be used in conjunction with ourstimulator compounds to advantage to obtain the beneficial effects of the multiple treatments; and, in some instances, to obtain greater stimulatory effects than can be obtained by the use of the active stimulator compounds by themselves.

The active compounds herein specifically named were found tohave little or no phytocidal effect. 7

Those skilled in the art will recognize that the use of the specified stimulator formulations in conjunction with or in addition to known seed treatment chemicals, such as fungicides, to obtain the beneficial effects of both treat ments, would be a logical extension and within the scope of the present invention.

What is claimed is:

1. A composition for stimulating plant seed germination and plant growth comprising as the active compound 12' present therein in an effective proportion a member of the class having the structural formula wherein Ar is a member of the group consisting of.

7 hydroxy phenyl, cyclohexyl, alkyl cyclohexyl, hydroxy 'resulted in a marked increase in acceleration of emergence.

cyclohexyl and alkyl hydroxy cyclohexyl radicals; X is a member of the group consisting of OH, -OOCR, OCOOR', -OCONR and atleast one hydrocarbon ether radical, the hydrocarbon being a member of the group consisting of alkyl and aryl radicals having 1 to 10 carbon atoms; R is a member of the group consisting of hydrogen, alkyl and aryl radicals having 1 to 10 carbon atoms; R is a member of the group consisting of alkyl and aryl radicals having 1 to 10 carbon atoms; and a phytologically acceptable carrier. substance selected from the group consisting of water wettable solid powders in dry form containing a surface active substance, dry plant and seed cohesive dusts containing a surface active agent, and emulsion concentrates containing a solid surface active agent and an aqueous solvent, adapting said composition for the treatment of seeds, roots and plants.

2. A composition as defined by claim 1 in which the active compound is a l,1,2-tris(4-methylphenyl) l,2-'

7. A composition as defined by claim 1 in which the' active compound is a l,l,2-tris(4-methylphenyl) 1,2- dideoxy-3,4,5,6-tetra-O-methyl hexitol.

8. A composition as defined by claim 1 in which the active compound is a l,l-bis(4-methylphenyl)-2-(3,4-di methylphenyl)-l,2-dideoxy hexitol.

9. A composition as defined by claim 1 in which the active compound is a 1,2-bis(4-methylphenyl)-1 (4-.

methylcyclohexyl)-1,2-dideoxy hexitol.

10. A composition as defined by claim 1 in which the active compound is a 1,1-bis(4-ethylphenyl) 2-(3,4dimethylphenyl) -1,2-dideoxy-3,4,5,6-tetra-O-acetyl hexitol.

11. A composition as defined by claim 1 in which the active compound is a 1,1,2-tris(3,4-dimethylphenyl)-1,2- dideoxy-3,4:5,6di-O-isopropylidine hexitol.

12. A composition as defined by claim 1 in which the 7 active compound is a 1,l,2-tris(4-methylphenyl) 1 ,2-

dideoxy-3,4:5,6-di-O-benzylidene hexitol.

13. A composition as defined by claim 1 in which the active compound is a 1,1,2-tris(3,4-dimethylphenyl)-l,2- dideoxy-3,4,5,6-tetra-O-methyl hexitol.

' 14. A composition as defined by claim 1 in which the active compound is a 1,1,2-tris(3,4-dimethy1phenyl) 1,2- dideoxy-3,4,5,6-tetra-O-(phenylcarbamoyl) hexitol.

15. A composition as defined by claim 1 in which the active com-pound is a 1,l,2-tris(4-methylphenyl)-l,2-dideoxy-5,6-di-O-methyl hexitol.

16. A composition as defined by claim 1 in which the active compound is a 1,l,2-tris(4-methylphenyl) 1,2- dideoxy-3,4-bis-O-(ethoxycarbony1)-5,6-cyclo O (carbonyl) hexitol.

17. A composition as defined by claim 1 in which the active compound is a 1,l,2-tri-phenyl-1,2-dideoxy hexitol.

18. A composition as defined by claim 1 in which the active compound is a 1,l,2-tris(4 ethylphenyl) 1,2- dideoxy hexitol.

19. A method for stimulating the germination of plant seeds, and the growth of roots and plants, which comprises treating the same with an efiective amount of a compound having the structural formula wherein Ar is a member of the group consisting of phenyl, alkyl phenyl, hydroxy phenyl and alkyl hydroxy phenyl radicals; Ar and Ar" are members of the group consisting of phenyl, alkyl phenyl, hydroxy phenyl, alkyl hydroxy phenyl, cyclohexyl, alkyl cyclohexyl, hydroxy cyclohexyl and alkyl hydroxy cyclohexyl radicals; X is a member of the group consisting of OH, O OCR, OCOOR, 'OCONR and at least one hydrocarbon ether radical, the hydrocarbon being a member of the group consisting of alkyl and aryl radicals having 1 to 10 carbon atoms; R is a member of the group consisting of hydrogen, alkyl and aryl radicals having 1 to 10 carbon atoms; R is a member of the group consisting of alkyl and aryl radicals having 1 to 10 carbon atoms.

20. The method of claim 19 wherein the compound is contained in a phytologically acceptable carrier substance selected from the group consisting of water wettable solid powders in dry form containing a surface active substance, dry plant :and seed cohesive dusts containing a surface active agent, and emulsion concentrates containing a solid surface active agent and an aqueous solvent, adapting said composition for the treatment of seeds, roots and plants.

References Cited UNITED STATES PATENTS 2,798,099 7/1957 Linn 260-618 2,798,100 7/1957 Linn 260-618 LEWIS GOTIS, Primary Examiner. JAMES O. THOMAS, JR., Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,331,678 July 18, 1967 Cecil C. Chappelow, Jr., et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below In the heading to the printed specification, line 3, for "PLANT GROWTHS" read PLANT GROWTH column 2, line 56, for "I" read II Signed and sealed this 23rd day of July 1968 (SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer 

1. A COMPOSITION FOR STIMULATING PLANT SEED GERMINATION AND PLANT GROWTH COMPRISING AS THE ACTIVE COMPOUND PRESENT THEREIN IN AN EFFECTIVE PROPORTION A MEMBER OF THE CLASS HAVING THE STRUCTURAL FORMULA 